Tight-Binding Models for Lone Pair, Heteroanionic Solids, and Application to Layered Oxyhalides

Abstract: We provide a methodology to understand materials with complex bonding patterns, and apply it to the example of heteroanionic and lone pair materials. We build a tight-binding model based on Wannier functions fitted on density functional theory results, followed by enforcing symmetry on the atomic orbital basis set, and finally connecting and disconnecting sets of orbitals from the tight-binding model to understand their individual contribution to the resulting materials properties. We apply this methodology to complex materials, namely BiOCl and Bi$_2$YO$_4$Cl - part of a broader class of materials investigated for their applications in photocatalysis and photoluminescence. Our methodology can be generalized and applied to a wide variety of other materials, including halide perovskites, and multiferroic materials. This methodology allows us to isolate the origin of key electronic features in these materials, including the role of the Bi lone pair-anion bonding interaction - key to photoluminescence in many materials. Finally, we investigate the role of the crystal structure, Chlorine and Oxygen orbital energy levels and bonding in determining the photostability of bismuth oxyhalides. Our methodology allows us to understand the functionality of complex materials in an intuitive and qualitative manner.